KR20200005045A - Flame retardant basalt fiber reinforced composite and manufacturing method - Google Patents

Abstract

The present invention relates to a fire-resistant basalt fiber reinforced composite, and to a manufacturing method of the fire-resistant basalt fiber reinforced composite, which comprises the steps of: preparing an epoxy resin; lowering the viscosity of the epoxy resin and adding a flame retardant additive to the epoxy resin having the lowered viscosity; manufacturing a resin mixture by adding a curing agent to the epoxy resin to which the flame retardant additive is added; preparing a basalt fabric; impregnating the resin mixture into the basalt fabric; and heat-compressing the basalt fabric impregnated with the resin mixture to manufacture the fire-resistant basalt fiber reinforced composite.

Description

Refractory basalt fiber reinforced composite and manufacturing method thereof {Flame retardant basalt fiber reinforced composite and manufacturing method}

TECHNICAL FIELD The present invention relates to a fireproof basalt fiber reinforced composite and a method for producing the same, in particular, a fireproof basalt comprising an epoxy resin impregnated in a basalt fabric, and an additive of ileite, basalt, coal ash, and talc in the epoxy resin. The present invention relates to a fiber reinforced composite and a method for producing the same.

As environmental issues, such as global warming due to continuous industrial development, are becoming more serious, the Intergovernmental Panel on Climate Change (IPCC) climate change agreement has set relevant environmental pollution regulations, including setting carbon dioxide reduction targets worldwide. Therefore, metal materials used in various fields requiring light weight and durability, such as buildings, facilities, component materials, shipbuilding, marine, and aircraft, are used as replaceable polymer materials, and their use is gradually increasing.

However, since the polymer material is an organic material based on carbon, hydrogen, and oxygen, when heat is applied to the polymer material and thermal decomposition of the polymer material occurs, a gaseous flammable vapor is generated, and the flammable vapor is Can react with oxygen in the air. While the combustible vapor is reacted with oxygen, heat is generated, and as the heat is transferred back to the polymer material, the polymer material may be burned. For this reason, the polymer material has a high combustion speed, and a large amount of toxic gas may be generated by the organic material while the polymer material is burned. Accordingly, a problem of human and physical loss occurs, and in order to solve such a problem, it is necessary to develop a polymer material having improved fire and flame retardant properties.

For example, Korean Patent Application Publication No. KR100443110B1 (Inventors: Kiuchi Yukiro, Ijimasatoshi, Teraji Makatsushi, Katayama Isao, Matsuya Suo, Otaken) includes an epoxy resin (A), a phenolic resin (B), and an inorganic filler ( An epoxy resin composition containing C) and a curing accelerator (D), wherein the content of the inorganic filler (C) in the cured product which contains no flame retardant or flame retardant aid and cures the composition is W (% by weight), When the bending modulus at 240 ± 20 ° C. of the cured product is set to E (kgf / mm 2), the bending modulus (E) becomes 0.015 W + 4.1 ≦ E ≦ 0.27 W + 21.8 when 30 ≦ W <60. Epoxy resin, characterized in that the numerical value, which is 0.30 W-13 ≤ E ≤ 3.7 W-184 when 60 ≤ W ≤ 95, wherein the cured product forms a foam layer during pyrolysis and ignition and exhibits flame retardancy. To initiate the composition The.

Lungol-based resins are known as resin materials having excellent fire resistance and flame retardant properties among thermosetting polymers. However, when the human body is exposed to the pulmonary resin, the protein in the human body and the pulmonary resin may react, causing various human diseases such as skin and respiratory diseases. Accordingly, the waste phenol resin is treated as a highly toxic substance and is currently prohibited from use.

Accordingly, while improving the fire resistance and flame retardancy of the polymer material itself, it is necessary to develop an environment-friendly flame retardant additive harmless to the human body and a flame retardant composite material using the same.

One technical problem to be solved by the present invention is to provide a refractory basalt fiber reinforced composite material with improved fire and flame retardant properties.

Another technical problem to be solved by the present invention is to provide a fire-resistant basalt fiber-reinforced composite comprising a flame-retardant additive that is harmless to humans and environmentally friendly.

Another technical problem to be solved by the present invention is to provide a method for producing a refractory basalt fiber reinforced composite material comprising a method of lowering the viscosity of an epoxy resin.

Another technical problem to be solved by the present invention is to provide a method for producing a refractory basalt fiber reinforced composite material comprising a flame retardant additive including ileum, basalt, coal ash, and talc.

Another technical problem to be solved by the present invention is to provide a method for producing a refractory basalt fiber-reinforced composite material comprising curing by reacting an epoxide ring of an epoxy resin with an amine group of a curing agent.

Another technical problem to be solved by the present invention is to provide a method for producing a refractory basalt fiber reinforced composite comprising a method of impregnating a resin mixture into a basalt fabric.

The technical problem to be solved by the present invention is not limited to the above.

In order to solve the above technical problem, the present invention provides a method for producing a refractory basalt fiber reinforced composite.

According to one embodiment, the method of manufacturing a refractory basalt fiber-reinforced composite, preparing an epoxy resin, heating the epoxy resin to lower the viscosity, adding a flame retardant additive to the epoxy resin having a lower viscosity, the flame retardant Adding a curing agent to the epoxy resin to which an additive has been added, preparing a resin mixture, preparing a basalt fabric, impregnating the resin mixture into the basalt fabric, and the basalt fabric impregnated with the resin mixture. By thermal compression, it may comprise the step of producing a refractory basalt fiber reinforced composite.

According to one embodiment, the flame retardant additive may include ileum, basalt, coal ash, and talc.

According to one embodiment, the step of adding the flame retardant additive, preparing ileum, basalt, and talc, using a jaw crusher, the primary crushed the ileum, the basalt and the talc To prepare a primary ileum powder, a primary basalt powder, and a primary talc powder, by using a disk miller, the primary ileum powder, the primary basalt powder, and the primary Talc powder secondary grinding, to prepare a secondary ileum powder, a secondary basalt powder, and a secondary talc powder, a wet milling process using a pot mill, the secondary ileum powder, Tertiary crushing of the secondary basalt powder, and the secondary talc powder to produce tertiary ileum powder, tertiary basalt powder, and tertiary talc powder; and to the epoxy resin, the tertiary ileum powder Adding the tertiary basalt powder and tertiary talc powder It may include the step.

According to one embodiment, the step of adding the flame retardant additive, may include the step of sifting the coal ash, to obtain a coal ash powder.

According to an embodiment, preparing the basalt fabric may include preparing basalt fibers extending in a first direction, and using the basalt fibers as weft, warp, or weft and warp yarns. Producing a basalt fabric.

According to one embodiment, the epoxy resin may be a non-halogen epoxy.

In order to solve the above technical problem, the present invention provides a refractory basalt fiber reinforced composite.

According to one embodiment, the refractory basalt fiber reinforced composite includes a basalt fabric, an epoxy resin impregnated in the basalt fabric, and a flame retardant additive provided in the epoxy resin and comprising ileum, basalt, coal ash, and talc. can do.

According to one embodiment, the refractory basalt fiber reinforced composite further includes a curing agent including an amine group, the epoxide ring of the epoxy resin and the amine group of the curing agent may include a cured.

According to an embodiment of the present invention, preparing an epoxy resin, lowering the viscosity of the epoxy resin and adding a flame retardant additive to the epoxy resin having a lower viscosity, by adding a curing agent to the epoxy resin to which the flame retardant additive is added Preparing a resin mixture, preparing a basalt fabric, impregnating the resin mixture into the basalt fabric, and thermocompressing the basalt fabric impregnated with the resin mixture to produce a refractory basalt fiber reinforced composite. There can be provided a method of making a refractory basalt fiber reinforced composite comprising the steps.

Accordingly, it is possible to provide a refractory basalt fiber reinforced composite including flame retardant additives that are both harmless to humans and environmentally friendly while improving fire and flame retardant properties.

1 is a flow chart illustrating a method of manufacturing a refractory basalt fiber reinforced composite according to an embodiment of the present invention.
2 is a graph showing a result of measuring the viscosity of the epoxy resin according to the ratio of the curing agent added to the epoxy resin according to an embodiment of the present invention.
3 is a photograph of the resin mixture according to Experimental Examples 1-1 to 1-3 and Comparative Example 1 of the present invention.
4 is a graph showing the flame retardant properties of the resin mixture according to Experimental Examples 1-1 to 1-3 and Comparative Example 1 of the present invention.
5 is a photograph of fire-resistant basalt fiber reinforced composites according to Experimental Examples 2-1 to 2-3, and Comparative Example 2 of the present invention.
6 is a graph showing the flame retardant properties of the refractory basalt fiber reinforced composite according to Experimental Examples 2-1 to 2-3, and Comparative Example 2 of the present invention.
7 is a photograph after the flame resistance test of the refractory basalt fiber reinforced composite according to Experimental Examples 3-1 to 3-7, and Comparative Example 3 of the present invention.
8 is a graph showing the flame retardant properties of the refractory basalt fiber reinforced composites according to Experimental Examples 3-1 to 3-7 and Comparative Example 3 of the present invention.
9 is a photograph after the flame resistance test of the refractory basalt fiber reinforced composite according to Experimental Examples 4-1 to 4-8, and Comparative Examples 4-1 and 4-2 of the present invention.
10 is a graph showing the flame retardant properties of refractory basalt fiber reinforced composites according to Experimental Examples 4-1 to 4-8, and Comparative Examples 4-1 and 4-2 of the present invention.
11 is a quantitative and qualitative analysis graph of the gas generated when measuring the cone calorimeter of the refractory basalt fiber reinforced composite prepared in 9: 1 ratio of the epoxy resin and the hardener according to an embodiment of the present invention.
12 is a quantitative and qualitative analysis graph of the gas generated when measuring the cone calorimeter of the refractory basalt fiber reinforced composite prepared in 8: 2 ratio of the epoxy resin and the curing agent according to an embodiment of the present invention.
FIG. 13 is flexural strength and Young's modulus data of a refractory basalt fiber reinforced composite prepared according to a ratio (9: 1 and 8: 2) of an epoxy resin and a curing agent according to an embodiment of the present invention.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, the technical idea of the present invention is not limited to the exemplary embodiments described herein and may be embodied in other forms. Rather, the embodiments introduced herein are provided to ensure that the disclosed contents are thorough and complete, and that the spirit of the present invention can be sufficiently delivered to those skilled in the art.

In the present specification, when a component is mentioned to be on another component, it means that it may be formed directly on the other component or a third component may be interposed therebetween. In addition, in the drawings, the thicknesses of films and regions are exaggerated for effective explanation of technical contents.

In addition, in various embodiments of the present specification, terms such as first, second, and third are used to describe various components, but these components should not be limited by these terms. These terms are only used to distinguish one component from another. Therefore, what is referred to as a first component in one embodiment may be referred to as a second component in another embodiment. Each embodiment described and illustrated herein also includes its complementary embodiment. In addition, the term 'and / or' is used herein to include at least one of the components listed before and after.

In the specification, the singular encompasses the plural unless the context clearly indicates otherwise. In addition, the terms "comprise" or "having" are intended to indicate that there is a feature, number, step, element, or combination thereof described in the specification, and one or more other features or numbers, steps, configurations It should not be understood to exclude the possibility of the presence or the addition of elements or combinations thereof.

In addition, in the following description of the present invention, if it is determined that a detailed description of a related known function or configuration may unnecessarily obscure the subject matter of the present invention, the detailed description thereof will be omitted.

Hereinafter, a method of manufacturing a refractory basalt fiber reinforced composite according to an embodiment of the present invention.

1 is a flow chart illustrating a method of manufacturing a refractory basalt fiber reinforced composite according to an embodiment of the present invention, Figure 2 is a viscosity of the epoxy resin according to the ratio of the curing agent added to the epoxy resin according to an embodiment of the present invention It is a graph showing the measurement results.

Referring to FIG. 1, an epoxy resin may be prepared (S110). According to an embodiment of the present invention, the epoxy resin may be a non-halogen epoxy. According to one embodiment, the viscosity and curing time of the epoxy resin may vary depending on the ratio of the curing agent added to the epoxy resin.

By heating the epoxy resin to lower the viscosity, a flame retardant additive may be added to the epoxy resin with a lower viscosity (S120). According to one embodiment, in the step of adding the flame retardant additive to the epoxy resin, the properties of the refractory basalt fiber-reinforced composite to be produced later may vary depending on the homogeneity of the flame retardant additive is dispersed in the epoxy resin. According to an embodiment of the present invention, by lowering the viscosity of the epoxy resin, and gradually put the flame retardant additive in the epoxy resin with a lower viscosity, the flame retardant additive may be dispersed homogeneously in the epoxy resin.

According to an embodiment of the present invention, the flame retardant additive may include natural minerals. Specifically, the natural minerals may include ileum, basalt, coal ash, and talc. According to an embodiment of the present invention, in order to examine the characteristics of the ileum, the basalt, the coal ash, and the talc used as the flame retardant additive, the ileum, the basalt, the coal ash, and included in the talc The result of analyzing the chemical component through XRF can be shown as Table 1 below.

Filler Type
(~ 325 Mesh) SiO ₂
(wt%) Al ₂ O ₃
(wt%) Fe ₂ O ₃
(wt%) CaO
(wt%) MgO
(wt%) K ₂ O
(wt%) Na ₂ O
(wt%) TiO ₂
(wt%) SO ₃
(wt%) Ig.loss
(wt%) Ileal cancer
(Anorthosite) 49.6 31.7 1.04 13.7 0.36 0.52 2.78 0.14 - - basalt
(Basalt) 43.7 16.4 12.5 9.12 11.4 1.70 3.43 0.99 - - Fly ash 57.0 17.8 5.38 5.32 2.29 1.15 2.05 0.82 0.59 3.77 Talc 52.8 7.37 8.01 1.80 27.2 1.65 0.22 0.18 - -

Referring to Table 1, the ileal cancer may have a high melting point, as it contains SiO ₂ and Al ₂ O ₃ in an amount of about 80 wt% or more. Accordingly, it can be used as an additive to improve fire resistance and flame retardancy. The basalt may have excellent heat resistance as Fe ₂ O ₃ , CaO, MgO and the like in a higher content than other raw materials, and may be used as an additive to improve the fire resistance and flame retardancy. The coal ash may have a high melting point as it contains SiO ₂ and Al ₂ O ₃ in an amount of about 75 wt% or more, and since other raw materials are bulky, the coal ash has a powder form, Since there is no need for an aftertreatment process such as grinding, there is an advantage that the process is simplified. The talc is a hydrated magnesium sheet silicate having the formula Mg ₃ Si-O- (OH) ₂ , having a molecular structure consisting of a layer of magnesium-oxygen / hydroxyl octahedron sandwiched between two layers of silicon-oxygen tetrahedron. Due to these structural properties, they may have excellent fire resistance and flame retardancy. In addition, SiO ₂ And By including MgO in an amount of at least about 80 wt%, it may likewise be excellent in fire resistance and flame retardancy.

As described above, the coal ash has a powder form, whereas the ileal rock, the basalt, and the talc have a lump form, so that the flame retardant additive may form the ileum rock, the basalt rock, and the talc. When included, the step of adding the flame retardant additive, the step of preparing the ileum, the basalt, and the talc, using a jaw crusher, the ileum, the basalt and the talc 1 Primary grinding to prepare primary ileum powder, primary basalt powder, and primary talc powder, using a disk miller, the primary ileum powder, the primary basalt powder, and the Secondary pulverization of the primary talc powder, to prepare the secondary ileum powder, the secondary basalt powder, and the secondary talc powder; a wet milling process using a pot mill, wherein the secondary ileum powder , The secondary string A third step of pulverizing the rock-free powder, and the secondary talc powder to prepare a tertiary ileum powder, a tertiary basalt powder, and a tertiary talc powder; and in the epoxy resin, the tertiary ileum powder, Tertiary basalt powder, and the tertiary talc powder may be added.

On the other hand, when the flame retardant additive includes the coal ash, adding the flame retardant additive, preparing the coal ash, sifting the coal ash, to obtain coal ash powder, and to the epoxy resin And adding the coal ash powder, and as described above, the coal ash having the form of a powder as the flame retardant additive, rather than adding the natural mineral other than the coal ash having a bulk form as the flame retardant additive. The step of adding may be simpler. The specific gravity of the coal ash may be lower than the specific gravity of the tertiary ileum rock powder, the tertiary basalt powder, and the tertiary active powder. Accordingly, according to one modification, after mixing the lime with the first epoxy resin, after mixing the tertiary ileum rock powder, the tertiary basalt powder, and the tertiary talc powder with a second epoxy resin, These can be mixed. In this case, the first epoxy resin may have a lower viscosity than the second epoxy resin. Alternatively, according to another modification, after the lime is added to the epoxy resin, the tertiary ileum rock powder, the tertiary basalt powder, and the tertiary talc powder may be added. For this reason, the coal ash, the tertiary ileum rock powder, the tertiary basalt powder, and the tertiary talc powder may be uniformly mixed with the epoxy resin in an easy manner.

According to one variation, before the coal ash, the tertiary ileum powder, the tertiary basalt powder, and the tertiary talc powder are added to the epoxy resin, the coal ash, the tertiary ileum powder, the tertiary A solvent is provided to the basalt powder, and the tertiary talc powder, and the coal ash provided with the solvent, the tertiary ileum powder, the tertiary basalt powder, and the tertiary talc powder may be added to the epoxy resin. . Accordingly, bubbles of the surface of the coal ash, the tertiary ileum rock powder, the tertiary basalt powder, and the tertiary talc powder may be efficiently removed, and a separate defoaming process may not be performed.

According to one variation, before the coal ash, the tertiary ileum powder, the tertiary basalt powder, and the tertiary talc powder are added to the epoxy resin, the coal ash, the tertiary ileum powder, the tertiary The basalt powder, and the tertiary talc powder, are agglomerated by a granulation process, and the composite aggregate of the coal ash, the tertiary ileum powder, the tertiary basalt powder, and the tertiary talc powder is added to the epoxy resin. Can be. In this case, in the granulation process, the limestone powder, the tertiary ileum powder, and the talc powder are first agglomerated, and then the tertiary basalt powder is provided to the tertiary basalt powder. It may be controlled to have a relatively high proportion at the surface of the aggregate, or the tertiary basalt powder constitutes the surface of the composite aggregate. Accordingly, as will be described later, when the resin mixture having the composite aggregate is impregnated into the basalt fabric, the adhesion of the composite aggregate to the basalt fabric can be improved.

A curing agent may be added to the epoxy resin to which the flame retardant additive is added, thereby preparing a resin mixture (S130). Referring to FIG. 2, a viscosity measurement result of the epoxy resin according to the ratio of the curing agent added to the epoxy resin to which the flame retardant additive is not added may be confirmed. The curing agent was added to the epoxy resin so that the ratio of the epoxy resin and the curing agent was 9: 1, 8: 2, and 7: 3, respectively. 2, it can be seen that as the ratio of the curing agent added to the epoxy resin increases, the viscosity of the epoxy resin increases.

However, depending on the proportion of the curing agent added to the epoxy resin, the degree to which the viscosity of the epoxy resin increases is small, so that the change in viscosity of the epoxy resin affects the later step of impregnating the resin mixture into the basalt fabric. This may be weak.

In order to identify the factors influencing the step of impregnating the resin mixture into the basalt fabric, the curing time of the epoxy resin was varied, depending on the proportion of the curing agent added to the epoxy resin. The curing time for each curing temperature of the epoxy resin according to the ratio of the curing agent added to the epoxy resin may be represented as shown in Table 2 below.

Mixing ratio


Curing temperature Epoxy Resin: Curing Agent 9: 1 8: 2 7: 3 150 ℃ 34 mins 19 mins 15 mins 160 ℃ 31 mins 16 mins 13 mins 170 ℃ 29 mins 13 mins 11 mins

 Referring to [Table 2], when the ratio of the epoxy resin and the curing agent is the same, it was difficult to observe that the change in the curing time according to the curing temperature is apparent, but the ratio of the curing agent added to the epoxy resin increases. It can be confirmed that the more time the epoxy resin is cured, the shorter it is. This may be a phenomenon due to the increase in the amine group capable of reacting with the epoxide ring through a stoichiometric reaction between the epoxide ring of the epoxy resin molecular structure and the amine group of the curing agent.

In the step of adding the curing agent to the epoxy resin to which the flame-retardant additive is added, the properties of the refractory basalt fiber-reinforced composite to be produced later vary depending on the homogeneity of the curing agent is dispersed in the epoxy resin to which the flame-retardant additive is added. Can be. According to an embodiment of the present invention, after lowering the viscosity of the epoxy resin and adding the flame retardant additive to the epoxy resin having a lower viscosity, the curing agent is gradually added and then stirred, and the epoxy resin to which the flame retardant additive is added is added. The curing agent may be uniformly dispersed in.

Basalt fabric can be prepared (S140). According to an embodiment of the present invention, preparing the basalt fabric may include preparing basalt fibers extending in a first direction, and using the basalt fibers as weft, warp, or weft and ramp. It may include the step of preparing the basalt fabric.

According to an embodiment, the basalt fibers may be manufactured by melting and basalt ore to prepare basalt filaments, and adjusting the tex or denier of the basalt filaments to suit the purpose.

According to an embodiment, the preparing of the basalt fibers may include: shaking the basalt fibers to spread the basalt fibers, and providing powdered nylon resin to the basalt fibers to spread the basalt fibers. Equalizing the spacing between the fibers.

According to one embodiment, spreading the basalt fibers, and providing a powdery nylon resin to the basalt fibers, the first step of spreading the basalt fibers, the first spreading basalt fibers 2 Difference spreading. After the secondary spreading step, the powdery nylon resin may be dispersed to allow basalt fibers to be spread at regular intervals by hot air.

The resin mixture may be impregnated into the basalt fabric (S150). According to an embodiment of the present invention, the step of impregnating the resin mixture on the basalt fabric may be performed through a hand lay-up process. However, when the talc is used as the flame retardant additive, it may be difficult to impregnate the basalt fabric with the resin mixture through a hand lay-up process. For example, in the case of the epoxy resin containing 40 wt% of the talc, as the viscosity of the epoxy resin increases, it may be difficult to impregnate the resin mixture into the basalt fabric through a hand lay-up process.

By heat-compressing the basalt fabric impregnated with the resin mixture, it is possible to manufacture a refractory basalt fiber reinforced composite (S160). According to an embodiment of the present disclosure, the thermal compression may be performed at 160 ° C. for 5 hours at 5 MPa.

Hereinafter, specific experimental examples for the refractory basalt fiber reinforced composite according to an embodiment of the present invention will be described.

Before manufacturing the refractory basalt fiber reinforced composite according to an embodiment of the present invention, in order to find out the flame retardant properties of the epoxy resin to which the flame retardant additive is used to prepare the refractory basalt fiber reinforced composite, the experiment of the present invention A resin mixture according to the example was prepared.

Preparation of Resin Mixture According to Experimental Example 1-1

An epoxy resin was prepared.

The viscosity of the epoxy resin was lowered, and 5 wt% of ileal rock was added to the epoxy resin having a lower viscosity as a flame retardant additive.

As a curing agent, 4,4'-Diaminodiphenylmethane (DDM) of Tokyo Chemical Industry Co., Ltd. was prepared.

At a temperature of 80 ° C., after adding the DDM to the epoxy resin so that the ratio of the epoxy resin added to the ileal arm and the DDM is 9: 1, 10 × 10 cm ² Poured into a metal mold of size and cured for 2 hours in an oven at 150 ℃ to prepare a resin mixture (FRepoxy5) according to Experimental Example 1-1.

Preparation of Resin Mixture According to Experimental Example 1-2

In Experimental Example 1-1 described above, 10 wt% of ileal rock was added as the flame retardant additive to prepare a resin mixture (FRepoxy10) according to Experimental Example 1-2.

Preparation of Resin Mixture According to Experimental Example 1-3

In Experimental Example 1-1 described above, 15 wt% of ileal rock was added as the flame retardant additive to prepare a resin mixture (FRepoxy15) according to Experimental Examples 1-3.

Preparation of Resin Mixture According to Comparative Example 1

In Experimental Example 1-1 described above, a resin mixture (1FRepoxy0) according to Comparative Example 1 was prepared without adding ileal cancer as the flame retardant additive.

Experimental Examples 1-1 to 1-3 of the present invention, and the resin mixture according to Comparative Example 1 can be arranged as shown in Table 3 below.

Sample Name Amount of ileum cancer Resin Mixture (FRepoxy5) According to Experimental Example 1-1 5 wt% Resin Mixture (FRepoxy10) According to Experimental Example 1-2 10 wt% Resin Mixture (FRepoxy15) According to Experimental Examples 1-3 15 wt% Resin mixture (1FRepoxy0) according to Comparative Example 1 0 wt%

Figure 3 is a photograph of the resin mixture according to Experimental Examples 1-1 to 1-3, and Comparative Example 1 of the present invention, Figure 4 is according to Experimental Examples 1-1 to 1-3, and Comparative Example 1 of the present invention A graph showing the flame retardant properties of the resin mixture.

3 and 4, in order to determine the flame retardant properties of the resin mixtures according to Experimental Examples 1-1 to 1-3, and Comparative Example 1 of the present invention, the resin mixtures were complexed at 750 ° C. in a cone calorimeter. Heat and smoke generated for 5 minutes (ISO 5660-1 standard flame retardant conditions). Flame retardant properties of the resin mixture according to Experimental Examples 1-1 to 1-3, and Comparative Example 1 of the present invention may be summarized as shown in Table 4 below.

Sample PHRR
(kW / m ² ) THR
(MJ / m ² ) SPR
(m ² / s) TSP
(m ² ) FRepoxy5 201.76 19.54 0.237 13.64 FRepoxy10 202.71 19.90 0.230 14.51 FRepoxy15 175.55 19.75 0.205 14.98 1FRepoxy0 220.79 20.95 0.258 15.04

 Referring to Table 4, the maximum heat release rate (PHRR), total heat release amount (THR), and smoke of the resin mixture according to Experimental Examples 1-1 to 1-3 of the present invention, rather than the resin mixture according to Comparative Example 1 It can be seen that the incidence rate (SPR), and the maximum value of total smoke generation amount (TSP) tend to decrease. In particular, the maximum value of the heat release rate and the smoke generation rate tends to decrease as the amount of ileal cancer added to the epoxy resin increases. .

Or more, to determine the flame retardant properties of the resin mixture according to the embodiment of the present invention, to determine the flame retardant properties of the fire-resistant basalt fiber-reinforced composite prepared based on the resin mixture, below, according to another embodiment of the present invention Specific experimental examples of basalt fiber reinforced composites are described.

Preparation of Refractory Basalt Fiber Reinforced Composites According to Experimental Example 2-1

A resin mixture (FRepoxy5) was prepared as in Experimental Example 1-1 described above.

Five basalt fabrics of 200 g / m ² were prepared.

Through a hand lay-up process, the resin mixture was impregnated into the basalt fabric.

The basalt fabric impregnated with the resin mixture was thermocompressed for 1 hour at 160 ° C. at 5 MPa to prepare a fire resistant basalt fiber reinforced composite (BF: FRepoxy5) according to Experimental Example 2-1 of 0.9 mm thickness.

Preparation of Refractory Basalt Fiber Reinforced Composites According to Experimental Example 2-2

A resin mixture (FRepoxy10) was prepared as in Experimental Example 1-2 described above.

Then, in the same manner as in Experimental Example 2-1 described above, a refractory basalt fiber reinforced composite (BF: FRepoxy10) according to Experimental Example 2-2 was prepared.

Preparation of Refractory Basalt Fiber Reinforced Composites According to Experimental Example 2-3

A resin mixture (FRepoxy15) was prepared as in Experimental Example 1-3 described above.

Then, in the same manner as in Experimental Example 2-1 described above, a refractory basalt fiber reinforced composite (BF: FRepoxy15) according to Experimental Example 2-3 was prepared.

Preparation of Refractory Basalt Fiber Reinforced Composites According to Comparative Example 2

A resin mixture (1FRepoxy0) was prepared as in Comparative Example 1 described above.

Then, in the same manner as in Experimental Example 2-1 described above, a refractory basalt fiber reinforced composite (2BF: FRepoxy0) according to Comparative Example 2 was prepared.

Refractory basalt fiber reinforced composite according to Experimental Examples 2-1 to 2-3, and Comparative Example 2 of the present invention can be summarized as shown in Table 5 below.

Sample Name Amount of ileum cancer
(wt%) thickness
(mm) Refractory basalt fiber reinforced composite according to Experimental Example 2-1 (BF: FRepoxy5) 5 0.9 Refractory basalt fiber reinforced composite according to Experimental Example 2-2 (BF: FRepoxy10) 10 Refractory basalt fiber reinforced composite according to Experimental Example 2-3 (BF: FRepoxy15) 15 Refractory basalt fiber reinforced composite according to Comparative Example 2 (2BF: FRepoxy0) N / A

5 is a photograph of the fire-resistant basalt fiber-reinforced composite according to Experimental Examples 2-1 to 2-3, and Comparative Example 2 of the present invention, and FIG. 6 is Experimental Examples 2-1 to 2-3, and Comparative Example of the present invention. It is a graph showing the flame retardant properties of the refractory basalt fiber reinforced composite according to 2.

5 and 6, to determine the flame retardant properties of the refractory basalt fiber reinforced composite according to Experimental Examples 2-1 to 2-3, and Comparative Example 2 of the present invention, The meter was ignited at 750 ° C. to measure heat and smoke generated for 5 minutes (ISO 5660-1 standard flame retardant conditions). Flame retardant properties of the refractory basalt fiber reinforced composite according to Experimental Examples 2-1 to 2-3, and Comparative Example 2 of the present invention can be summarized as shown in Table 6 below.

Sample PHRR
(kW / m ² ) THR
(MJ / m ² ) SPR
(m ² / s) TSP
(m ² ) BF: FRepoxy5 104.70 9.24 0.1016 6.63 BF: FRepoxy10 97.68 9.32 0.098 6.58 BF: FRepoxy15 92.94 9.46 0.091 8.82 2BF: FRepoxy0 117.48 11.50 0.1097 7.20

 Referring to Table 6, the maximum heat release rate, total heat release amount, and smoke of the refractory basalt fiber reinforced composite according to Experimental Examples 2-1 to 2-3 of the present invention, rather than the refractory basalt fiber reinforced composite according to Comparative Example 2 It can be seen that the incidence rate and the maximum value of total smoke generation tend to decrease. Like the resin mixtures according to Experimental Examples 1-1 to 1-3 of the present invention, the maximum value of the heat release rate and the smoke generation rate tends to decrease as the amount of the ileal cancer added to the epoxy resin increases. When the ileal cancer is added, it can be seen that the flame retardant properties are improved.

In the above, the flame retardant properties of the refractory basalt fiber reinforced composite according to an embodiment of the present invention have been examined, and specific experimental examples of the refractory basalt fiber reinforced composite according to another embodiment of the present invention will be described.

Preparation of Refractory Basalt Fiber Reinforced Composites According to Experimental Example 3-1

In Experimental Example 1-1 described above, 10 wt% of ileal rock was added as a flame retardant additive.

In Experimental Example 2-1 described above, three basalt fabrics of 600 g / m ² were prepared to prepare a refractory basalt fiber reinforced composite (FRepoxy_Anorthosite10) according to Experimental Example 3-1 having a thickness of 1.1 to 1.2 mm.

Preparation of Refractory Basalt Fiber Reinforced Composites According to Experimental Example 3-2

In Experimental Example 3-1 described above, 10 wt% of basalt was added as a flame retardant additive to prepare a refractory basalt fiber reinforced composite (FRepoxy_Basalt10) according to Experimental Example 3-2.

Preparation of Refractory Basalt Fiber Reinforced Composites According to Experimental Example 3-3

In Experimental Example 3-1 described above, 10 wt% of coal ash was added as a flame retardant additive to prepare a refractory basalt fiber reinforced composite (FRepoxy_Ash10) according to Experimental Example 3-3.

Preparation of Refractory Basalt Fiber Reinforced Composites According to Experimental Example 3-4

In Experimental Example 3-1 described above, 10 wt% of talc was added as a flame retardant additive to prepare a refractory basalt fiber reinforced composite (FRepoxy_Talc10) according to Experimental Example 3-4.

Preparation of Refractory Basalt Fiber Reinforced Composites According to Experimental Examples 3-5

In Experimental Example 3-1 described above, fire retardant basalt fiber-reinforced composite (FRepoxy_Anorthosite40) according to Experimental Example 3-5 of thickness 1.3-1.5 mm was prepared by adding 40 wt% of ileal rock as a flame retardant additive.

Preparation of Refractory Basalt Fiber Reinforced Composites According to Experimental Example 3-6

In Experimental Example 3-1 described above, 40 wt% of basalt was added as a flame retardant additive to prepare a refractory basalt fiber reinforced composite (FRepoxy_Basalt40) according to Experimental Example 3-6.

Preparation of Refractory Basalt Fiber Reinforced Composites According to Experimental Example 3-7

In Experimental Example 3-1 described above, fire retardant basalt fiber-reinforced composite (FRepoxy_Ash40) according to Experimental Example 3-7 was prepared by adding 40 wt% of coal ash as a flame retardant additive.

Preparation of Refractory Basalt Fiber Reinforced Composites According to Comparative Example 3

In Comparative Example 2 described above, three basalt fabrics of 600 g / m ² were prepared to prepare a refractory basalt fiber reinforced composite (3FRepoxy0) according to Comparative Example 3 having a thickness of 1.0 mm.

Refractory basalt fiber reinforced composite according to Experimental Examples 3-1 to 3-7, and Comparative Example 3 of the present invention can be summarized as shown in Table 7 below.

Sample Name Additive amount (wt%) thickness
(mm) Refractory basalt fiber reinforced composite according to Experimental Example 3-1 (FRepoxy_Anorthosite10) Ileal cancer 10 1.1 to 1.2 Refractory basalt fiber reinforced composite according to Experimental Example 3-2 (FRepoxy_Basalt10) Basalt 10 Refractory basalt fiber reinforced composite according to Experimental Example 3-3 (FRepoxy_Ash10) Fly Ash 10 Refractory basalt fiber reinforced composite according to Experimental Example 3-4 (FRepoxy_Talc10) Talc 10 Refractory basalt fiber-reinforced composite according to Experimental Examples 3-5 (FRepoxy_Anorthosite40) Ileum cancer 40 1.3 to 1.5 Refractory basalt fiber reinforced composite according to Experimental Example 3-6 (FRepoxy_Basalt40) Basalt 40 Refractory basalt fiber reinforced composite according to Experimental Example 3-7 (FRepoxy_Ash40) Fly Ash 40 Refractory basalt fiber reinforced composite according to comparative example 3 (3FRepoxy0) N / A 1.0

7 is a photograph after the flame retardancy test of the refractory basalt fiber reinforced composite according to Experimental Examples 3-1 to 3-7, and Comparative Example 3 of the present invention, Figure 8 is Experimental Examples 3-1 to 3-7 of the present invention, And a flame retardant characteristic of the refractory basalt fiber reinforced composite material according to Comparative Example 3.

7 and 8, to determine the flame retardant properties of the refractory basalt fiber reinforced composite according to Experimental Examples 3-1 to 3-7, and Comparative Example 3 of the present invention, the refractory basalt fiber reinforced composites The meter was ignited at 750 ° C. to measure heat and smoke generated for 5 minutes (ISO 5660-1 standard flame retardant conditions). Flame retardant properties of the refractory basalt fiber reinforced composite according to Experimental Examples 3-1 to 3-7, and Comparative Example 3 of the present invention can be summarized as shown in Table 8 below.

Sample R / C Value Flame Retardant Properties TTI
(sec.) PHRR
(kW / m ² ) THR
(MJ / m ² ) SPR
(m ² / s) TSP
(m ² ) Mass loss
(%) FRepoxy_Anorthosite10 23.73 29 70.862 5.247 0.0719 5.481 14.83 FRepoxy_Basalt10 20.35 25 66.961 5.044 0.0678 5.488 14.04 FRepoxy_Ash10 15.09 30 39.871 4.155 0.0657 6.822 14.62 FRepoxy_Talc10 23.40 24 69.492 4.844 0.059 3.54 13.62 FRepoxy_Anorthosite40 33.33 33 94.031 6.956 0.0925 5.887 16.24 FRepoxy_Basalt40 34.31 29 87.897 6.928 0.081 4.685 15.27 FRepoxy_Ash40 33.82 34 62.037 6.702 0.0949 9.219 18.38 3FRepoxy0 14.28 16 48.797 3.715 0.0442 4.13 10.58

 Referring to Table 8, the weight of the refractory basalt fiber-reinforced composites was measured before and after the flame retardancy test to further confirm how the change in R / C value affects the fire and flame retardant properties. As a result, when the content of the flame retardant additive added to the epoxy resin increases, it can be observed that the R / C value of the refractory basalt fiber reinforced composite increases. In addition, when the content of the flame retardant additive added to the epoxy resin increases, it can be observed that the ignition time (TTI) of the refractory basalt fiber reinforced composite increases.

Through Table 8, the characteristics according to the type of the flame retardant additives, ileum, basalt, coal ash, and talc are all flame retardant additives to improve the fire and flame retardant properties of the refractory basalt fiber-reinforced composite, among them coal ash It can be seen that the fire and flame retardant properties of the refractory basalt fiber reinforced composite material is the most excellent when added as the flame retardant additive. However, in the case of coal ash, since the fine carbon powder is burned, it can be confirmed that in terms of smoke generation, it shows a higher value than other flame retardant additives.

According to the relative grade table (refer to [Table 9] below) showing the flame retardant criteria by flame propagation at home and abroad using the Limited Oxygen Index (LOI), Experimental Examples 3-1 to 3-7, and The flame retardant grades of the refractory basalt fiber reinforced composites according to Comparative Example 3 were investigated.

Korean Ministry of Construction and Transportation European Union United Kingdom (BS) United States (ASTM) Remarks Notice 476 Notice 438 ranking LOI standard ranking LOI standard ranking LOI standard ranking LOI standard ranking LOI standard Flame retardant class 1 Nonflammable Applied separately  A1 Nonflammable Separate standard Separate standard Flame retardant class 2 Semi-non-flammable A2 Semi-non-flammable Flame retardant class 3 42-17% B 40% or more Class0 40% or more none Risk 4 35% or more C 32% or more Class1 32% or more ClassA 32% or more International Building Interior Fire Retardant Class 1 Risk 3 32% or more Risk 2 28% or more D 28% or more Class2 28% or more Class B 28% or more Flame retardant class 2 Risk 1 24% or more E 24% or more Class3 24% or more ClassC 24% or more Self-extinguishing

The limit oxygen index is measured when the specimen to be measured vertically is placed inside a glass tube maintaining a room temperature, and then the inside of the glass tube is formed in a mixed atmosphere of nitrogen and oxygen, and the flame is ignited at the top of the specimen. This is the minimum oxygen concentration when the flame is completely extinguished before 3 minutes have elapsed without spreading below the specimen, or when half of the specimen burns into the flame for 3 minutes, and can be calculated as shown in Equation 1 below. .

<Equation 1>

LOI = [O ₂ ] / ([N ₂ ] + [O ₂ ]) X 100

That is, the limit oxygen index relatively evaluates the combustibility of a material, and the larger the limit oxygen index, the more difficult it is to burn. In general, substances with a critical oxygen index value of 26 or greater are evaluated as self extinguishing materials. Limit oxygen index is measured using the standard of ASTM D2863

Evaluation results of the marginal oxygen index of the refractory basalt fiber reinforced composite according to Experimental Examples 3-1 to 3-7, and Comparative Example 3 of the present invention can be summarized as shown in Table 10 and Table 11 below.

FRepoxy_
Anorthosite10 Oxygen Conc. (%) 40 45 50 55 49 48 48.5 48.9 48.6 Self-Extinguishment O O X X X O O X X FRepoxy_
Basalt10 Oxygen Conc. (%) 40 45 50 48 49 48.5 48.7 48.8 Self-Extinguishment O O X O C O O X FRepoxy_
Fly Ash10 Oxygen Conc. (%) 40 45 50 53 55 54 53.5 53.2 53.1 Self-Extinguishment O O O O X X X X X FRepoxy_
Talc10 Oxygen Conc. (%) 40 45 50 48.5 47.5 48 48.3 48.4 Self-Extinguishment O O X X O O O O FRepoxy_
Anorthosite40 Oxygen Conc. (%) 40 45 44 44.5 44.2 44.4 Self-Extinguishment O X O X O O FRepoxy_
Basalt40 Oxygen Conc. (%) 40 45 45.8 45.3 45.6 45.7 Self-Extinguishment O X X O O O FRepoxy_
Fly Ash40 Oxygen Conc. (%) 40 45 50 48 47 46 46.5 46.3 46.1 46.2 Self-Extinguishment O O X X X O X X O O 3FRepoxy0 Oxygen Conc. (%) 40 45 50 55 57 56 55.5 55.3 55.1 Self-Extinguishment O O O O X X X X X

Sample FRepoxy_
Anorthosite10 FRepoxy_
Basalt10 FRepoxy_
Fly Ash10 FRepoxy_
Talc10 FRepoxy_
Anorthosite40 FRepoxy_
Basalt40 FRepoxy_
Fly Ash40 3FRepoxy0 LOI (%) 48.5 48.7 53 48.4 44.4 45.7 46.2 55

 Referring to [Table 10] and [Table 11], the fireproof basalt fiber reinforced composites according to Experimental Examples 3-1 to 3-7 of the present invention are the highest grades of flame retardant standards by flame propagation standards at home and abroad shown in [Table 9]. By showing 40% or more of the limit oxygen index standard, it turns out that it has the outstanding flame-retardant characteristic.

However, as the amount of the flame retardant additive added to the epoxy resin increases, the decrease in the limit oxygen index value of the refractory basalt fiber reinforced composite is caused by the difference in R / C value and thickness of the refractory basalt fiber reinforced composite. As a phenomenon, it can be solved by making the R / C value and thickness of the refractory basalt fiber reinforced composite uniform in the actual production process.

Through Table 10 and Table 11, as the fire and flame retardant properties of the fire-resistant basalt fiber-reinforced composites according to Experimental Examples 3-3 and 3-7 of the present invention are the most excellent, using coal ash as a flame-retardant additive In this case, as described above, it is possible to provide a refractory basalt fiber-reinforced composite which is economical as well as having excellent fire and flame retardant properties as it does not require post-treatment processes such as grinding and refining processes.

Or more, the flame-retardant properties of the fire-resistant basalt fiber-reinforced composite according to the embodiment of the present invention, and to determine the properties of the fire-resistant basalt fiber-reinforced composite according to the ratio of the curing agent added to the epoxy resin, Specific experimental examples of the refractory basalt fiber reinforced composite according to another embodiment will be described.

Preparation of Refractory Basalt Fiber Reinforced Composites According to Experimental Example 4-1

In Experimental Example 3-1 described above, 2 wt% of ileal rock was added as a flame retardant additive to prepare a refractory basalt fiber reinforced composite (9: 1_Anorthosite2) according to Experimental Example 4-1.

Preparation of Refractory Basalt Fiber Reinforced Composites According to Experimental Example 4-2

In Experimental Example 4-1 described above, 3 wt% of ileal rock was added as a flame retardant additive to prepare a refractory basalt fiber reinforced composite (9: 1_Anorthosite3) according to Experimental Example 4-2.

Preparation of Refractory Basalt Fiber Reinforced Composites According to Experimental Example 4-3

In Experimental Example 4-1 described above, 5 wt% of ileal rock was added as a flame retardant additive to prepare a refractory basalt fiber reinforced composite (9: 1_Anorthosite5) according to Experimental Example 4-3.

Preparation of Refractory Basalt Fiber Reinforced Composites According to Experimental Example 4-4

In Experimental Example 4-1 described above, 10 wt% of ileal rock was added as a flame retardant additive to prepare a refractory basalt fiber reinforced composite (9: 1_Anorthosite10) according to Experimental Example 4-4.

Preparation of Refractory Basalt Fiber Reinforced Composites according to Comparative Example 4-1

In Experimental Example 4-1 described above, a refractory basalt fiber reinforced composite (9: 1_Anorthosite0) according to Comparative Example 4-1 was prepared without adding a flame retardant additive.

Preparation of Refractory Basalt Fiber Reinforced Composites According to Experimental Example 4-5

In Experimental Example 4-1 described above, the curing agent was added to the epoxy resin so that the ratio of the epoxy resin and the curing agent was 8: 2, and the refractory basalt fiber reinforced composite material according to Experimental Example 4-5 (8: 2_Anorthosite2 ) Was prepared.

Preparation of Refractory Basalt Fiber Reinforced Composites According to Experimental Example 4-6

In Experimental Example 4-5 described above, 3 wt% of ileal rock was added as a flame retardant additive to prepare a refractory basalt fiber reinforced composite (8: 2_Anorthosite3) according to Experimental Example 4-6.

Preparation of Refractory Basalt Fiber Reinforced Composites According to Experimental Example 4-7

In Experimental Example 4-5 described above, 5 wt% of basalt was added as a flame retardant additive to prepare a refractory basalt fiber reinforced composite (8: 2_Anorthosite5) according to Experimental Example 4-7.

Preparation of Refractory Basalt Fiber Reinforced Composites According to Experimental Example 4-8

In Experimental Example 4-5 described above, 10 wt% of ileal rock was added as a flame retardant additive to prepare a refractory basalt fiber reinforced composite (8: 2_Anorthosite10) according to Experimental Example 4-8.

Preparation of Refractory Basalt Fiber Reinforced Composites according to Comparative Example 4-2

In Experimental Example 4-5 described above, a refractory basalt fiber reinforced composite (8: 2_Anorthosite0) according to Comparative Example 4-2 was prepared without adding a flame retardant additive.

Refractory basalt fiber reinforced composites according to Experimental Examples 4-1 to 4-8, and Comparative Examples 4-1 and 4-2 of the present invention may be arranged as shown in Table 12 below.

Sample Name Amount of ileum cancer (wt%) Epoxy resin
Hardener ratio thickness
(mm) Refractory basalt fiber reinforced composite according to Experimental Example 4-1 (9: 1_Anorthosite2) 2 9: 1 1.1 to 1.2 Refractory basalt fiber-reinforced composite according to Experimental Example 4-2 (9: 1_Anorthosite3) 3 Refractory basalt fiber reinforced composite according to Experimental Example 4-3 (9: 1_Anorthosite5) 5 Refractory basalt fiber-reinforced composite according to Experimental Example 4-4 (9: 1_Anorthosite10) 10 Refractory basalt fiber reinforced composite according to Comparative Example 4-1 (9: 1_Anorthosite0) N / A Refractory basalt fiber reinforced composite according to Experimental Example 4-5 (8: 2_Anorthosite2) 2 8: 2 Refractory basalt fiber-reinforced composite according to Experimental Example 4-6 (8: 2_Anorthosite3) 3 Refractory basalt fiber reinforced composite according to Experimental Example 4-7 (8: 2_Anorthosite5) 5 Refractory basalt fiber-reinforced composite according to Experimental Example 4-8 (8: 2_Anorthosite10) 10 Refractory basalt fiber reinforced composite according to Comparative Example 4-2 (8: 2_Anorthosite0) N / A

Figure 9 is a photograph after the flame retardancy test of the refractory basalt fiber reinforced composite according to Experimental Examples 4-1 to 4-8, and Comparative Examples 4-1 and 4-2 of the present invention, Figure 10 is Experimental Example 4- of the present invention It is a graph which shows the flame-retardant property of the refractory basalt fiber reinforced composites from 1 to 4-8 and Comparative Examples 4-1 and 4-2.

9 and 10, in order to determine the flame retardant properties of the refractory basalt fiber reinforced composite according to Experimental Examples 4-1 to 4-8, and Comparative Examples 4-1 and 4-2 of the present invention, the refractory basalt The fiber reinforced composites were ignited at 750 ° C. in a cone calorimeter to measure the heat and smoke generated for 5 minutes (ISO 5660-1 standard flame retardant condition). Flame retardant properties of the refractory basalt fiber reinforced composite according to Experimental Examples 3-1 to 3-7, and Comparative Example 3 of the present invention can be summarized as shown in Table 13 below.

Sample R / C Value Flame Retardant Properties TTI
(sec.) PHRR
(kW / m ² ) THR
(MJ / m ² ) SPR
(m ² / s) TSP
(m ² ) Mass loss
(%) 9: 1_Anorthosite2 12.62 35 33.416 3.769 0.0622 8.628 13.59 9: 1_Anorthosite3 13.17 36 32.446 3.829 0.0585 6.638 15.05 9: 1_Anorthosite5 16.28 36 41.007 4.629 0.0622 8.14 14.42 9: 1_Anorthosite10 18.26 40 35.563 4.011 0.053 6.208 11.81 9: 1_Anorthosite0 11.50 36 29.36 3.35 0.0532 7.674 9.85 8: 2_Anorthosite2 15.29 44 31.685 3.789 0.0563 6.709 12.26 8: 2_Anorthosite3 14.45 36 36.741 4.503 0.0561 6.568 11.90 8: 2_Anorthosite5 17.77 45 41.106 4.641 0.0669 7.424 13.70 8: 2_Anorthosite10 18.29 46 46.482 5.164 0.0606 7.424 13.70 8: 2_Anorthosite0 14.29 38 25.659 2.74 0.0452 6.812 10.95

Referring to [Table 13], when the ratio of the epoxy resin and the flame retardant additive is 8: 2 rather than 9: 1, it can be observed that the R / C value of the refractory basalt fiber reinforced composite increased. . In addition, when the content of ileal rock as the flame retardant additive added to the epoxy resin is increased, it can be observed that the ignition time (TTI) of the refractory basalt fiber reinforced composite increases due to the influence of the flame retardant additive. .

In other words, when the content of the flame retardant additive added to the epoxy resin is increased, it can be seen that the flame retardant properties of the refractory basalt fiber reinforced composite is improved.

11 is a quantitative and qualitative analysis graph of the gas generated when measuring the cone calorimeter of the refractory basalt fiber reinforced composite prepared in 9: 1 ratio of the epoxy resin and the hardener according to an embodiment of the present invention, and FIG. Epoxy resin and hardener according to an embodiment of the present invention is a quantitative and qualitative analysis of the gas generated when measuring the cone calorimeter of the refractory basalt fiber reinforced composite prepared at 8: 2.

11 and 12, the flame retardant properties of the refractory basalt fiber reinforced composite according to an embodiment of the present invention can be summarized as shown in Table 14 below.

Sample Maximum Concentration (Gas Analysis) CO
(ppm) NO _x
(ppm) HCN
(ppm) SO ₂
(ppm) HCl
(ppm) 9: 1_Anorthosite2 457 6 2 36 3 9: 1_Anorthosite3 358 6 One 28 3 9: 1_Anorthosite5 453 8 3 33 4 9: 1_Anorthosite10 348 6 2 23 3 9: 1_Anorthosite0 323 4 2 23 4 8: 2_Anorthosite2 356 6 One 27 2 8: 2_Anorthosite3 385 9 3 32 2 8: 2_Anorthosite5 476 9 One 40 2 8: 2_Anorthosite10 491 10 One 42 One 8: 2_Anorthosite0 282 6 3 21 One

Referring to [Table 14], it can be confirmed that the refractory basalt fiber reinforced composite material according to the embodiment of the present invention satisfies the standard value of the IMO Part 2 condition (MSC.61 (67)) of [Table 15] below. .

division standard Toxicity test
(ppm) Evaluation item CO = 1,450 HCN = 140 HCl = 600 NO _X = 350 SO ₂ (* 200 or less surface) = 120

Similarly, according to the relative grade table (see [Table 9]), which shows the flame retardancy criteria due to flame propagation at home and abroad using the Limited Oxygen Index (LOI), Experimental Examples 4-1 to 4-8, And the results of evaluating the marginal oxygen index of the refractory basalt fiber reinforced composites according to Comparative Examples 4-1 and 4-2 can be summarized as shown in Table 16 and Table 17 below.

9: 1_Anorthosite2 Oxygen Conc. (%) 45 50 55 60 62 61 60.5 60.2 60.1 Self-Extinguishment O O O O X X X X O 9: 1_Anorthosite3 Oxygen Conc. (%) 45 50 55 60 57 56 55.5 55.2 55.1 Self-Extinguishment O O O X X X X X X 9: 1_Anorthosite5 Oxygen Conc. (%) 40 45 50 48.5 47.5 48 48.1 48.4 48.3 Self-Extinguishment O O X X O O O X O 9: 1_Anorthosite10 Oxygen Conc. (%) 45 50 55 53 51.5 50.7 50.3 50.1 Self-Extinguishment O O X X X X X X 9: 1_Anorthosite0 Oxygen Conc. (%) 40 45 50 55 57 56 55.8 55.9 Self-Extinguishment O O O O X X O O 8: 2_Anorthosite2 Oxygen Conc. (%) 45 50 55 60 65 63 64 63.5 63.3 63.1 Self-Extinguishment O O O O X O X X X X 8: 2_Anorthosite3 Oxygen Conc. (%) 55 60 65 63 64 63.4 63.2 63.1 Self-Extinguishment O O X O X X X O 8: 2_Anorthosite5 Oxygen Conc. (%) 55 60 65 63 64 64.5 64.2 64.1 Self-Extinguishment O O X O O X X X 8: 2_Anorthosite10 Oxygen Conc. (%) 55 60 65 63 61 62 61.4 61.2 61.1 Self-Extinguishment O O X X O X X X X 8: 2_Anorthosite0 Oxygen Conc. (%) 60 65 70 75 80 77.5 79 79.5 79.7 79.9 Self-Extinguishment O O O O X O O O O O

Sample 9: 1_
Anorthosite2 9: 1_
Anorthosite3 9: 1_
Anorthosite5 9: 1_
Anorthosite10 9: 1_
Anorthosite0 LOI (%) 60.1 55 48.3 50 55.9 Sample 8: 2_Anorthosite2 8: 2_
Anorthosite3 8: 2_
Anorthosite5 8: 2_
Anorthosite10 8: 2_
Anorthosite0 LOI (%) 63 63.1 64 61 79.9

Referring to [Table 16] and [Table 17], the fireproof basalt fiber-reinforced composite materials according to Experimental Examples 4-1 to 4-8 of the present invention are the highest grades of flame retardant standards by flame propagation standards at home and abroad shown in [Table 9]. By showing 40% or more of the limit oxygen index standard, it turns out that it has the outstanding flame-retardant characteristic.

In addition, through [Table 16] and [Table 17], Experimental Examples 4-5 to 4 of the present invention than the limit oxygen index value of the refractory basalt fiber reinforced composite according to Experimental Examples 4-1 to 4-4 of the present invention. It can be seen that the limit oxygen index value of the refractory basalt fiber reinforced composite according to -8 is larger. Accordingly, when the content of the curing agent added to the epoxy resin is increased, it can be seen that due to the influence of the flame retardant additives, the fire and flame retardant properties of the fire resistant basalt fiber reinforced composites are improved.

FIG. 13 is flexural strength and Young's modulus data of a refractory basalt fiber reinforced composite prepared according to a ratio (9: 1 and 8: 2) of an epoxy resin and a curing agent according to an embodiment of the present invention.

Flexural strength of the refractory basalt fiber reinforced composite according to Experimental Examples 4-1 to 4-8, and Comparative Examples 4-1 and 4-2 of the present invention was measured according to the ASTM D790-10 standard. To measure the flexural strength, the refractory basalt fiber reinforced composite was prepared with a width of 20 mm and a thickness of 1.1 mm. The flexural strength of the refractory basalt fiber reinforced composite was measured using <Equation 2> below at a speed of 1 mm / min at a support span of 20 mm (L), and the following refractory basalt fiber reinforced using <Equation 3> below. Flexural modulus of the composite was measured.

<Equation 2>

Flexural Strength (σ _f ) = 3FL / 2bd ²

<Equation 3>

Flexural Modulus (E _f ) = L ³ m / 4bd ³

Flexural strength test and Young's modulus results of the refractory basalt fiber reinforced composites according to Experimental Examples 4-1 to 4-8, and Comparative Examples 4-1 and 4-2 of the present invention can be summarized as shown in Table 18 below.

Sample Mechanical test Flexural strength
(MPa) Young's modulus
(GPa) 9: 1_Anorthosite0 81.54 (± 7.07) 8.78 (± 0.46) 9: 1_Anorthosite2 102.63 (± 8.54) 11.80 (± 0.35) 9: 1_Anorthosite3 183.12 (± 13.37) 18.47 (± 0.86) 9: 1_Anorthosite5 94.01 (± 6.39) 9.91 (± 0.40) 9: 1_Anorthosite10 171.94 (± 9.20) 19.65 (± 0.54) 8: 2_Anorthosite0 123.70 (± 5.73) 14.18 (± 0.52) 8: 2_Anorthosite2 129.07 (± 11.90) 16.63 (± 0.70) 8: 2_Anorthosite3 319.77 (± 17.68) 24.89 (± 0.24) 8: 2_Anorthosite5 138.68 (± 6.77) 16.05 (± 0.87) 8: 2_Anorthosite10 162.34 (± 10.93) 18.77 (± 0.51)

Referring to [Table 18], it can be seen that the flexural strength of the refractory basalt fiber reinforced composite according to Experimental Example 4-2 of the present invention increased more than the refractory basalt fiber reinforced composite according to Experimental Example 4-1 of the present invention. However, it can be seen that the flexural strength of the refractory basalt fiber reinforced composite according to Experimental Example 4-3 of the present invention was reduced. In other words, the refractory basalt fiber reinforced composite according to the embodiment of the present invention means that the flame retardant additive added to the epoxy resin has the best flexural strength when it contains more than 2 wt% and less than 5 wt%. .

Further, the flexural strength of the refractory basalt fiber reinforced composites according to Experimental Examples 4-5 to 4-8 of the present invention is higher than the flexural strength of the refractory basalt fiber reinforced composites according to Experimental Examples 4-1 to 4-4 of the present invention. Through, it can be seen that as the amount of the curing agent added to the epoxy resin increases, the flexural strength of the refractory basalt fiber reinforced composite increases.

This is due to the curing reaction of the epoxide ring of the epoxy resin and the amine group of the curing agent, and as the ratio of the curing agent added to the epoxy resin increases, there are more amine groups that can be cured and more curing proceeds. This may be a phenomenon.

The flexural strength value of the steel grating of PermaStruct, which is currently commercially available, is 280 MPa, and the physical properties of the refractory basalt fiber reinforced composite according to Experimental Example 4-6 of the present invention are comparable to this.

In the above, the method of manufacturing the refractory basalt fiber reinforced composite according to the embodiment of the present invention, and the characteristics of the refractory basalt fiber reinforced composite prepared by the method have been described in detail. Although the present invention has been described in detail using the preferred embodiments, the scope of the present invention is not limited to the specific embodiments, it should be interpreted by the appended claims. In addition, those skilled in the art should understand that many modifications and variations are possible without departing from the scope of the present invention.

Claims (8)

Preparing an epoxy resin;
Lowering the viscosity of the epoxy resin and adding a flame retardant additive to the lowered epoxy resin;
Preparing a resin mixture by adding a curing agent to the epoxy resin to which the flame retardant additive is added;
Preparing a basalt fabric;
Impregnating the resin mixture into the basalt fabric; And
Thermocompressing the basalt fabric impregnated with the resin mixture to produce a refractory basalt fiber reinforced composite.
According to claim 1,
The flame retardant additive is a method for producing a fire-resistant basalt fiber-reinforced composite comprising ileum, basalt, coal ash, and talc.
The method of claim 2,
Adding the flame retardant additive,
Preparing ileum, basalt, and talc;
Using a jaw crusher to primary crush the ileum, the basalt and the talc to produce a primary ileum powder, a primary basalt powder, and a primary talc powder;
Using a disk miller, the primary ileum powder, the primary basalt powder, and the primary talc powder are pulverized secondary, so that the secondary ileum powder, secondary basalt powder, and secondary talc Preparing a powder;
In a wet grinding process using a pot mill, the secondary ileum powder, the secondary basalt powder, and the secondary talc powder are pulverized by tertiary, tertiary ileum powder, tertiary basalt powder, and Preparing a tertiary talc powder; And
And adding the tertiary ileum rock powder, the tertiary basalt powder, and the tertiary talc powder to the epoxy resin.
The method of claim 2,
The step of adding the flame retardant additive, sifting the coal ash, to obtain a coal ash powder method of producing a refractory basalt fiber reinforced composite.
According to claim 1,
Preparing the basalt fabric,
Preparing basalt fibers extending in a first direction; And
Manufacturing the basalt fabric using the basalt fibers as weft, warp, or weft and warp yarns.
According to claim 1,
The epoxy resin is a method of producing a refractory basalt fiber reinforced composite comprising a non-halogen epoxy.
Basalt fabrics;
An epoxy resin impregnated into the basalt fabric; And
A refractory basalt fiber reinforced composite provided in said epoxy resin and comprising a flame retardant additive comprising ileum, basalt, coal ash, and talc.
The method of claim 7, wherein
Further comprising a curing agent comprising an amine group,
Refractory basalt fiber reinforced composite material containing what hardened | cured by reacting the epoxide ring of the said epoxy resin and the amine group of the said hardening | curing agent.

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